Aromatic polyalkylene ether sulphonates



Patented Nov. 7, 1939 UNITED STATES V 2,178,830 PATENT OFFICE AROMATIC POLYALKYLENE ETHEE SULPHONATES Herman A. Bruson, Philadelphia, Pa.,

assignor to Riihm & Haas Company, Philadelphia, Pa.

No Drawinga, Application April 26, 1938, Serial No. 204,306

16 Claims.

in which A is an aliphatic or cycloaliphatic hydrocarbon group, A is hydrogen or an aliphatic, cycloaliphatic, aromatic, arylaliphatic hydrocarbon or alkoxy group, R is an aromatic nucleus of the benzene, naphthalene, anthracene, phenanthrene or other condensed ring series, CnH2n is short chain alkylene radical having at least two carbon atoms, :cis an integer of 1 to 5 inclusive and y is 1 or 2. The total number of aliphatic carbon atoms in groups A and A should be at least four. Thus, if A is an aliphatic hydrocarbon group containing four or more carbon atoms, A maybe hydrogen but is not necessarily so. If, on the other hand, A contains less than four carbon atoms, then A must be an aliphatic or cycloaliphatic hydrocarbon radical containing at least enough aliphatic carbon atoms so that the total of such carbon atoms in A and A is at least four. This is necessary in order to maintain the balance between lipophilic and hydrophilic groups required for imparting capillary activity to the final product.

In the foregoing formula A may represent such groups as ethyl, propyl, butyl, amyl, hexyl, octyl, dodecyl, tetradecyl, hexadecyl, octadecyl, oleyl, or cycloaliphatic groups such as butyl-cyclohexyl, octyl-cyclohexyl, lauryl-cyclohexyl, cetyl-cyclohexyl, etc. or other alkyl group containing up to 30 carbon atoms; or bornyl, decahydronaphthyl, abietyl, tetrahydroabietyl or other terpenic radical or naphthenic radical. The alkyl groups mentioned above may have straight or branched chains and the OCnH2n-group of the formula may be attached to a primary, secondary or tertiary carbon atom. A may also represent unsaturated groups corresponding to the saturated groups enumerated. A may represent hydrogen, an alkyl group such as ethyl, butyl, amyl and the other alkyl and cycloalkyl groups represented by A or it may represent an aromatic or aryl aliphatic hydrocarbon group such as phenyl, benzyl, phenylethyl,phenylisobuty1 and the like.

The alkylene group represented by --CnH2n contains at least two carbon atoms and may be a straight or-branched chain radical such as are represented by the formulas:

n being an integer of from 2 to 5.

The new compounds provided by the present invention may be prepared in either of the fol-- lowing ways:

(a) An aliphatic, cycloaliphatic or terpenic alcohol whose hydrocarbon radical corresponds to A in the formula may be condensed with an aromatic alkylene ether halide having the formula in which X is a halogen atom, in the presence of an alkali metal oxide or hydroxide so as to split out alkali metal halide; or the alkali alcoholate of the alcohol AOH may be condensed directly with the aromatic alkylene ether halide,-

again splitting out the alkali metal halide. The product thus obtained is then sulfonated by means of any of the usual sulfonating agents and, if desired, converted to any of its metal or organic base salts such as those of the alkali or alkaline earth metals, the primary, secondary or tertiary amines, for example, the methyl amines, ethyl and ethanol amines, pyridine, piperidine, etc.v

(b) A phenolic compound corresponding to the formula A'-ROH may be condensed with an aliphatic of cycloaliphatic alkylene ether halide in the presence of an alkali so as to split out the alkali metal halide. These products may also be sulfonated, and the sulfonic acids obtained converted to salts of various bases as described under (a).

In either of the foregoing methods the aromatic radical may be sulfonated prior to condensation but in such cases it will, of. course, be necessary to neutralize the sulfonic acid before it can be condensed in an alkaline solution with the Example 1 In a vessel fitted with an efiicient stirrer and reflux condenser a mixture consisting of 100 g. of p-phenoxy-p'-chlorodiethyl ether,

. and filtered.

CsH5O-CH2CH2OCH2CH2-OC12H2s It was a colorless oil'which, on redistillation,

boiled at 210-220 C./2-3 mm. The yield was.

The material was sulfonated by treating 35 g.

dissolved in 35 g. of ethylene dichloride with 23.2 g. of chlorsulfonic acid at 5 to 15 'C. for 24 hours,-with stirring. The dark oil was neutralized with dilute caustic soda. and evaporated to dryness. The product was a white mass which was readily soluble in water to give a foamy, soaplike solution. It gave-no precipitate with calcium chloride solution, and can be used in hard water as a dispersing, emulsifying or wetting agent.

Example 2 A mixture consisting of 156 g. of p-a, any, '7- tetramethyl-butylphenoxy-ethoxyethyl chloride, 93 g. of lauryl alcohol, and 22 g. of sodium hydroxide was heated for 7 hours at 190 to 200 C., as described in, Example 1. boiling at 250-265 C./3 mm., was collected as a colorless oil having the formula:

cm on. om-c-om-oOo-cnrcni-o-cni-cnt-o-cnHii 46.2 g. of this compound was sulfonated at 15' to 25 C. for 3 hours in 50 g. of ethylene dichloride, with 12.1 g. of chlorsulfonic acid, and neutralized with aqueous sodium hydroxide to give a foamy, soapy solution which, when dried, gave a white, waxy mass suitable as a dispersing'agent.

Example 3 A mixture consisting of 100 g. of p-phenoxy-p'- chlorodiethyl ether, 134 g. of oleyl alcohol and 30.8 g. of potassium hydroxide was heated with stirring under reflux for 15 hours at 190 to 220 C. After filtering 011 the precipitate, the filtrate was distilled in vacuo. The oil, boiling at 210- 240 C./0.1 mm., was collected as the desired 7 product of the probable formula:

CsH5-O--CH2CH2.-OCH2CH2O CHa-(CHz) 1-CH=CH(CH2) "l--CH3 A solution of 86 g. of the above product in 50 g. of ethylene dichloride was sulfonated at 5 to 10 C. with 46.4 g. of chlorsulfonic acid for 4 hours.

The product was neutralized with potassium hydroxide'solution and evaporated to dryness in vacuo. Product was a water-soluble, waxy mass useful as an emulsifying agent.

The analogous compound made from cetyl alcohol, namely:

csnt-o-cnscnko-cnicns-o -cisms gave a similar product upon sulfonation.

Example 4 A mixture consisting of 135.5 g. of lauryl phenol, 90.5 g. of p-butoxy-fi-chlorodiethyl ether, 20.5 g. of sodium hydroxide, 50 g. of ethyl alcohol and The desired product,-

10 g. of water was boiled under refiux for 10 hours withvigorous agitation. When cool, the product was filtered and the filtrate was distilled. under reduced pressure. Thedesired product, 'p- (laurylphenoxy-)-p'-butoxy diethyl ether.

distilled over at 212-220 c;/4 mm. as a colorless oil. Yield 40.6 g. of this product was treated at 5 C. with 20.6 g. of 98% sulfuric acid for several hoursand finally heated 3 hours at 70 C. The reaction mixture was then neutralized with dilute potassium hydroxide solution and evaporatedto dryness. sulfonated product formed a pasty mass having powerful emulsifying properties in aqueous solution.

Example-5 A mixture consisting of 103 g. of p-u, a, 'y, 'y-

tetramethyl-butylphenol, 90.5 g. of B-butoxy-p'a: chlorodiethyl ether, 20.5 g. of sodium hydroxide,

50 g. of ethyl alcohol, and l0 cc. of' water was boiled under reflux with stirring for12 hours at- C. The product, when cool, was filtered,'and

the filtrate distilled under reduced pressure. The fraction boiling at 205-210 C./4 .mm. came over as a colorless oil having the formula 35 g. of the above ether was sulfonated with 20.6 g. of 98% sulfuric acid at 50'-to 60 C. until the product became soluble in water (3 hours). The material obtained was then neutralized with potassium hydroxide. An aqueous solution of this sulfonate is useful as a dispersing agent for dyes.

Example 6 A mixture consisting of 85 g. of p-phenylphenol, 91 g. of ,8-butoxy-p'-chlorodiethyl ether, 20.5 g. of caustic soda, 50 g. of ethyl alcohol, and 10 cc. of water was heated with agitationunder reflux at90 C. for 12 hours. The material was cooled,

filtered, and the filtrate distilled. The product, boiling at 227-232 C./4 mm. is butoxy-ethomethoxy-diphenyl, having the probable formula can-o-cmcm-o-omcm-oQ-O Upon sulfonation by heating with 1 mol equivalent of chlorsulfonic acid at 50 0., a water-soluble capillary-active sulfonic acid is obtained having useful properties as a wetting agent.

Example 7 A mixture consisting of 88 g. of p-cyclohexylphenol, 90.5 g. of p-butoxy-p chlorodiethyl ether, 20.5 g. of caustic soda, 50 g. of butanol, and 10 cc. of water was boiled under reflux for 12 hours. The material was cooled, filtered, and the filtrate distilled. The product, boiling at 210-215 C./5 mm., weighed g., and is butoxyethoxyethoxyphenylcyclohexane, having the probable formula O cini-o-cnicnro-cnicBro-0511.

Upon sulfonation with concentrated sulfuric acid at 60 to 70 C., a water-soluble capillaryactive sull'onate is obtained which, in the form of its ammonium salt, is useful as a dispersing agent.

Example 8' A. mixture consisting of 90.5 g. of p-butoxy-K- chlorodiethyl ether, 72 g. of p-naphthoL- 20.5 g.

of caustic soda, 50 g. of butanol, and 10 .cc. of water was boiled for 12 hours under reflux. The cooled, filtered product was distilled in vacuo. 72 g. of fl-butoxy-ethoxyethoxynaphthalene, boiling at 221-230 C./5 mm. was obtained, having the formula Upon sulfonation with 1 mol equivalent of chlorsulfonic acid at 50 to 60 C., a water-soluble sulfonate, useful in the form .of its sodium salt as a dispersing agent for pigments, is obtained.

Example 9 A mixture consisting of 103 g. of p-ter.octy1- phenol (made by condensing diisobutylene and phenol), 54 g. of fi-chlorodiethyl ether, 20.5 g. of caustic soda, 50 g. of butanol, and 10 cc. of water was boiled under reflux for 10 hours. The cooled, filtered product yielded, upon distillation, '70 g. of the ether having the formula boiling at -157 C./2 mm. as a colorless oil. This compound was sulfonated with excess concentrated sulfuric acid at 50 to 60 C. yielding a water-soluble capillary-active sulfonate useful as a wetting agent.

Example 10 The compound CsH5OCH2CH2O--CH2 CH2OC10H17 (B.P. 185-195 C./3 mm. made by condensing borneol in the presence of caustic soda with p-phenoxy-fi'-chlorodiethyl ether was sulfonated at 50 C. with excess 98% sulfuric acid, and the product neutralized with potassium hydroxide. The water-soluble potassium sulfonate thus obtained is useful as a wetting-out agent for cotton.

' Example 11 A mixture, consisting of 178 g.'of p-oz,a,'y,'y-t6tramethyl-butylphenoxy-ethoxyethoxyethyl chloride C8H1"!C6H4-0CH2CH2O 21 g. of sodium hydroxide, and 81 g. of diethylene glycol monobutyl ether, was heated with stirring for 10 hours at 180 to 210 C., under reflux. The reaction product was washed and fractionally distilled in vacuo. The product reflux with stirring for 10 hours at 230 to 240 C. The reaction product was washed and distilled in vacuo. The product ning and throwing oils, cutting oils, insecticides,

finishing compounds containing waxes and oils; for dispersing pigments and dyes for rubber, inks and leather finishes; in cleaning operations for windows, floors, walls; removing residues of insecticide sprays from fruit, de-inking of newsprint, removing dust from the air in air-conditioning systems; in plating baths for deposition of nickel, tin, chromium, cadmium and other metals to give bright deposits and prevent pinholeing; as wetting or spreading agents for insecticides, parasiticides, fungicides, and pest repellents on plants, animals, fabrics, wood; for increasing the absorptive power of paper towels and cotton; and for breaking petroleum emulsions. It has also been found that these compounds have a definite fungicidal and bactericidal action.

Aromatic polyalkylene others, which on sulfonation yield the capillary-active materials described herein, are the subject matter of application Serial No. 204,307 filed on even date herewith.

I claim:

1. Compounds, which in the acid form have the general formula A(OC,.H:,.),OR

in which A represents a member of the group consisting of aliphatic and cycloaliphatic hydrocarbon radicals, A represents a member of the group consisting of hydrogen, aliphatic, cycloaliphatic, aryl and arylaliphatic hydrocarbon radicals, the sum of the aliphatic carbon atoms in A and A being at least four, R is an aromatic nucleus, C1|.H2n is an alkylene group containcame over at 262-280 C./3 mm. as a pale yellow oil, which upon redistillation boiled at 260-265 C./3 mm. Upon sulfonation with concentrated sulfuric acid at 50 to 60 CI, it yielded a watersoluble sulfonic acid which, after neutralization with diethanolamine, formed a good dispersing agent for pigments.

Example 12 A mixture consisting of 68 g. of p-a,a,'y,'y-tetramethylbutylphenoxyisopropoxy isoproply chloride,

C8H1'l-C6H4--OCH2CH.

(CH3)OCH(CH3) CHzCl 324 g. of diethylene glycol monobutyl ether, and 11.7 g. of potassium hydroxide was heated under ing from two to five carbon atoms inclusive, :1: is an integer from 1 to 5 inclusive and y is one of the integers 1 and 2.

2. Compounds, which in the acid form have the general formula A-(0CHCHs)=0R in which A represents a member of the group consisting of aliphatic and cycloaliphatic hydrocarbon radicals, A represents a member of the group consisting of hydrogen, aliphatic, cycloaliphatic, aryl and arylaliphatic hydrocarbon radicals, the sum of the aliphatic carbon atoms in A and A being at least four, R is an aromatic nu- 70 the general formula cleui| is an integer from l to 5 inclusive and y is oneofthe integers land 2.

v 3. Gompounds, which in the acid form have the formula a-o-onlcnro-omong-o a a oar). in which A represents a member of the group 10 consisting of aliphatic and cycloaliphatic hydrocarbon radicals, A represents a member of the group consisting of hydrogen, aliphatic, cycloaliphatic, aryl and arylaliphatic hydrocarbon radicals, the sum of the aliphatic carbon atoms in A 15 and A being at least four, R is an aromatic necleus and y is one of the integers 1 and 2. Y

4. Compounds, which in the acid form have the general formula (soin in which A represents a member of the group consisting of aliphatic and cycloaliphatic hydro- 25 carbon radicals, A represents a member of the group consisting of hydrogen, aliphatic, cycloaliphatic, aryl and arylaliphatic hydrocarbon radicals, the sum of the aliphatic carbon atoms in A and A being at least four, R is an aromatic 3o nucleus and y is one of the integers 1 and 2.

5. Compounds, which in the acid form have the v general formula A(O'CI-I 2CHz)aORSO3H in which A is an aliphatic hydrocarbon radical 35 containing at least fourcarbon atoms, .1: is an integer of from 1 to 5 inclusive and R. is a benzene nucleus.

6. Lauryloxy-ethoxy-cthoxy-ethoxyphenyi sulfonic acid OC2H4 OCcH4SO3H 7. Oleyloxy-ethoxy-ethoxy-phenyl sulfcnic acid 8. Cetyloxy-ethoxy-ethoxyphenyl sulfonic acid 9. The process for producing compounds of the 50 general formula 55 in which A represents a member of the group consisting of aliphatic and cycloaliphatic hydrocarbon radicals, A represents a member of the group consisting of hydrogen, aliphatic, cycloaliphatic, aryl and arylaliphatic hydrocarbon radi- 60 cals, the sum of the aliphatic carbon atoms in A and A being at least four, R is an aromatic nucleus, C1:H2n is an alkylene group containing from two to five carbon atoms inclusive, 2: is an integer from 1 to 5 inclusive and y is one of the g integers 1 and 2, which comprises treating an aromatic ether of the general formula A-(O-(hHhh-O-R-A with a sulfonating agent.

10. The process for producing compounds of in which A represents a member of the group,

consisting of aliphatic and cycloaliphatic hydrocarbon radicals, A represents a member of the group consisting of hydrogen, aliphatic, cycloali- .phatic, aryl and arylaliphatic hydrocarbon radicals, the sum of the aliphatic carbon atoms in A and A being at least four, R is an aromatic nucleus, :1: is an \integer from 1 to 5 inclusive and 1! is one of the integers 1 and 2, which comprises treating an' aromatic ether of the general formula A(OC1|.H2n) O-RA' with a sulfonating agent.

11. The process for producing compounds of the general formula i I a-o-omom-o-omcm-o4c soar the general formula v in which A represents a member of the group consisting of aliphatic and cycloaliphatic hydro carbon radicals, A represents a member of the group consisting of hydrogen, aliphatic, cycloaliphatic, aryl and arylaliphatic hydrocarbon radicals, the sum of the aliphatic carbon atoms in A and A being at least four, R is an aromatic nucleus, and y is one of the integers 1 and 2, which comprises treating an aromatic ether of the general formula with a sulfonating agent. 13. The process for producing compounds the general formula in which A is an aliphatic hydrocarbon radical containing at least four carbon atoms, :1: is an integer of from 1 to inclusive and R is a benzene nucleus, which comprises treating an aromatic ether of the general formula with a sulfonating agent.

14. The process. which comprises treating lauryloxy-ethoxyethoxy-ethoxy benzene with a sulfonating agent.

15. The process which comprises treating oleyloxy-ethoxyethoxy benzene with a sulfonating agent.

16. The process which comprises treating cetyloxy-ethoxyethoxy benzene with a sulfonating agent.

HERMAN A. BRUSON. 

